Hydrogen Sulfide → 2-(2',6'-Dichloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedione

HRID 46785Notes

Reaction equation

HRID 46785 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[CH:5]=[C:4]([Cl:11])[C:3]=1[CH:12]1[C:17](=[O:18])[CH2:16][C:15]([CH3:20])([CH3:19])[CH2:14][C:13]1=[O:21].S>[NH4+].[OH-].C(O)C>[Cl:1][C:2]1[CH:7]=[C:6]([NH2:8])[CH:5]=[C:4]([Cl:11])[C:3]=1[CH:12]1[C:17](=[O:18])[CH2:16][C:15]([CH3:19])([CH3:20])[CH2:14][C:13]1=[O:21]

Participants

5

Reactant 2

HCID 402Hydrogen Sulfide2×HCID 128766212-(2',6'-Dichloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione

Product 1

HCID 136881202-(2',6'-Dichloro-4'-aminophenyl)-5,5-dimethyl-1,3-cyclohexanedioneYield 45.1%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 14923Ammonium HydroxideSolvent

Procedure

A solution of 20.0 g (0.0606 mol) of 2-(2',6'-dichloro-4'-nitrophenyl)-5,5-dimethyl-1,3-cyclohexanedione in 150 ml conc. NH4OH and 150 ml of ethanol was stirred at room temperature while passing H2S gas through the solution at such a rate that all of the H2S was absorbed. After the solution was saturated with H2S, it was refluxed 24 hours while continuously passing H2S slowly through the solution. The reaction mixture was cooled to room temperature, the precipitated sulfur removed by filtration, and the filtrate evaporated to dryness under reduced pressure. To the residue was added 300 ml of 0.25 N NaOH, and the solution filtered once more. The filtrate was cooled and acidified to pH=4 with 6 N HCl. A tan solid formed which was collected by filtration to give 11.2 g when dry. This material was washed with methylene chloride to give 8.2 g (45%) of 2-(2',6'-dichloro-4'-aminophenyl)-5,5-dimethyl-1, 3-cyclohexanedione as a white powder, m.p. 243° d.

Workup

  1. customwas absorbed
  2. temperaturewas refluxed 24 hours while continuously passing H2S slowly through the solution
  3. customthe precipitated sulfur removed by filtration
  4. customthe filtrate evaporated to dryness under reduced pressure
  5. additionTo the residue was added 300 ml of 0.25 N NaOH
  6. filtrationthe solution filtered once more
  7. temperatureThe filtrate was cooled
  8. customA tan solid formed which
  9. filtrationwas collected by filtration
  10. customto give 11.2 g when
  11. customdry
  12. washThis material was washed with methylene chloride

Sources & evidence

ORD record
ord-b1f43075e129401b9083bd0b82423764
Source dataset
uspto-grants-1979_11
Patent number
US04175135

Reaction notes

Loading…